CN110965124A - Method for preparing high-quality calcium sulfate whiskers and calcium oxide by using industrial byproduct gypsum - Google Patents
Method for preparing high-quality calcium sulfate whiskers and calcium oxide by using industrial byproduct gypsum Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
Abstract
The invention discloses a method for preparing high-quality calcium sulfate whiskers and calcium oxide by using industrial by-product gypsum, belonging to the field of resource application of the industrial by-product gypsum. Preparing a suspension from pretreated gypsum, adding bicarbonate and ammonia water into the suspension, filtering to obtain calcium carbonate, adding water and hydrochloric acid into the obtained filtrate, adding a habit modifier and an organic active agent into the acidified reaction liquid to form an acidified composite crystal-transferring solution, adding the pretreated gypsum into the solution, reacting, filtering, washing and drying to obtain the calcium sulfate whisker. The process has wide and simple raw material sources, changes industrial by-product gypsum into calcium sulfate whisker, calcium oxide and the like, generates high value-added products, and obtains calcium oxide with the purity of more than 99 percent and the calcium sulfate whisker with the purity of more than 99 percent and the length-diameter ratio of 150-160.
Description
Technical Field
The invention relates to the field of resource application of industrial byproduct gypsum, and relates to a method for preparing high-quality calcium sulfate whiskers and calcium oxide by using the industrial byproduct gypsum.
Background
With the rapid development of the industries such as electric power, chemical engineering and the like in China, the industrial byproduct gypsum such as desulfurized gypsum, phosphogypsum, fluorgypsum and the like is increased day by day, the accumulation of the industrial byproduct gypsum occupies a large amount of space resources, and meanwhile, the industrial byproduct gypsum has negative influence on the environment, and how to develop and utilize the industrial byproduct gypsum becomes the focus of the attention of national governments and scientific and technological workers.
The industrial by-product gypsum is applied and popularized in the fields of cement retarder production, gypsum plaster board manufacturing, high-strength gypsum powder, cementing materials and the like with high efficiency. However, the utilization rate of the industrial by-product gypsum is still low in the whole view, and new technologies and new products with more valuable prospects need to be continuously developed. The gypsum whisker is a fibrous single crystal which is formed by calcium sulfate under specific conditions and preferentially grows in the axial direction, has uniform cross section area, complete appearance and internal structure, has the advantages of high strength, high modulus, high toughness, high temperature resistance, acid and alkali resistance and the like, integrates the advantages of reinforcing fiber and superfine inorganic filler, has strong affinity with polymer, and can be used as a reinforcing and toughening agent or a functional filler in resin, plastic, rubber, papermaking, friction and sealing materials; but also can be directly used as a filter material, a heat insulation material, a fire-resistant heat insulation material and the like.
CN 103628142B provides a method for preparing phosphogypsum whiskers by secondary crystallization, which comprises the steps of weighing dried phosphogypsum, adding a sulfuric acid solution, stirring and reacting in water bath, filtering while the solution is hot, removing insoluble substances, cooling and crystallizing at the room temperature of a filtrate, and keeping a filter cake after suction filtration; and adding a sulfuric acid solution and a crystallization assistant agent magnesium salt, stirring in a water bath for reaction, naturally cooling and crystallizing the solution in the water bath, performing suction filtration to obtain whiskers, washing to be neutral, and drying to obtain the calcium sulfate whiskers. CN 102745923B provides a method for preparing calcium sulfate whiskers by recrystallization, which comprises the steps of putting a raw material of which the main component is calcium sulfate into a sulfuric acid solution, stirring, heating to 60-95 ℃, drying a washed solid-phase product at a certain temperature to obtain calcium sulfate dihydrate whiskers, cooling to room temperature, carrying out solid-liquid separation on a suspension, and washing the separated solid-phase product. CN 109402720A proposes a method for preparing anhydrous calcium sulfate whisker from industrial by-product gypsum, mixing the industrial by-product gypsum with a certain amount of acid solution with the concentration of 20-30%, heating to a certain temperature to dissolve calcium sulfate in the gypsum, filtering while hot, and adjusting the pH value of the filtrate; adding a crystal transformation agent into the filtrate. Then transferring the filtrate into a reaction kettle, reacting for a certain time under certain reaction temperature and pressure conditions, quickly filtering and dehydrating, and transferring the prepared crystal whisker into a high-temperature furnace for roasting to obtain the anhydrous calcium sulfate crystal whisker. CN 102303883B proposes a method for preparing calcium oxide and sulfur by double-atmosphere fluidized roasting of desulfurized gypsum, wherein the aged desulfurized gypsum is dried and dehydrated, and enters a multistage suspension heat exchanger for preheating, the preheated thermal gypsum is sent into a circulating fluidized bed decomposing furnace, and primary air and secondary air are introduced for decomposition to obtain calcium oxide.
The calcium sulfate crystal whisker prepared by the method has the problems of poor purity, low length-diameter ratio, complex process, harsh temperature and pressure conditions and the like, and the method for preparing calcium oxide also has the problems of low purity, high energy consumption and the like. At present, no method for simultaneously preparing high-quality calcium sulfate whiskers and calcium oxide by using industrial by-product gypsum exists, and the comprehensive utilization rate of the industrial by-product gypsum is lower than 80% when the calcium sulfate whiskers or the calcium oxide is singly prepared, and the reaction conditions need high temperature or high pressure and the like. Therefore, it is necessary to provide a technical method for improving the comprehensive utilization rate and diversified utilization modes of gypsum.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for preparing high-quality calcium sulfate whiskers and calcium oxide by using industrial by-product gypsum.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing high-quality calcium sulfate whisker and calcium oxide by using industrial byproduct gypsum comprises the following steps:
1) pretreatment: washing industrial byproduct gypsum with water, and adding a grinding medium into the washed gypsum for ball milling; adding a hydrochloric acid solution for dissolving after ball milling, adding an organic solvent for extraction and separation after dissolving, and then recrystallizing to obtain pretreated gypsum;
2) preparation of calcium oxide: adding water into the pretreated gypsum in the step 1) and uniformly stirring to prepare suspension; adding bicarbonate and ammonia water into the suspension, reacting for 1-3 hours under the stirring condition of 100-200r/min, filtering after the reaction is completed, and filtering to obtain filtrate for later use; washing and drying the precipitate in sequence to obtain calcium carbonate, and calcining the calcium carbonate to obtain calcium oxide;
3) preparing calcium sulfate whiskers: adding water and hydrochloric acid into the filtrate obtained in the step 2), adding a habit modifier, an organic active agent and a solvent into the acidified reaction liquid to form an acidified composite crystal transformation solution, adding pretreated gypsum into the acidified composite crystal transformation solution, reacting for 1-5 hours at the temperature of 100-150 ℃ and the rotating speed of 100-500 r/min, performing ultrasonic action, and then filtering, washing and drying to obtain the calcium sulfate whisker.
The technical scheme of the invention is as follows: the adding amount of the grinding medium in the step 1) is 2-3 times of the mass of the industrial byproduct gypsum, the grinding time is 4-10 hours, and the average particle size of the ground gypsum is less than 30 mu m.
The technical scheme of the invention is as follows: in the step 1), the organic solvent is one or more of tributyl phosphate, n-octanol or tri-n-octylamine.
The technical scheme of the invention is as follows: the mass ratio of the gypsum to the water pretreated in the step 2) is 1: 2-1: 5.
the technical scheme of the invention is as follows: the mol ratio of the gypsum, the bicarbonate and the ammonia water after pretreatment in the step 2) is 1: 1.15: 1.2, adding the bicarbonate solution with the concentration of 0.2-1mol/L, wherein the concentration of ammonia water is 0.1-1mol/L, and the reaction temperature is 40-60 ℃.
The technical scheme of the invention is as follows: the calcination temperature of the calcium carbonate in the step 2) is 850-1000 ℃.
The technical scheme of the invention is as follows: the bicarbonate is one or more of ammonium bicarbonate, sodium bicarbonate and potassium bicarbonate.
The technical scheme of the invention is as follows: the pH value of the reaction solution after acidification in the step 3) is 1-2.
The technical scheme of the invention is as follows: in the step 3), the medium crystal agent is one or more of magnesium chloride, zinc chloride or copper chloride, and the addition amount is 5-20 wt% of the acidified reaction liquid; the organic activator is one or more of polyethylene glycol, polypropylene glycol or methoxy polyethylene glycol, and the addition amount is 1 to 5 weight percent of the acidified reaction liquid.
The technical scheme of the invention is as follows: the mass ratio of the gypsum pretreated in the step (3) to the acidified composite crystal transformation solution is 1: 10-50 min, and the ultrasonic action time is 10-30 min.
The invention has the beneficial effects that:
(1) the pretreatment of the industrial by-product gypsum can remove the impurity phase in the gypsum as much as possible, and the gypsum particles have uniform and refined shapes. Provides basic conditions for preparing high-quality calcium sulfate whiskers and calcium oxide, and realizes that the comprehensive utilization rate of industrial byproduct gypsum reaches more than 85%.
(2) Firstly, preparing high-purity calcium oxide by combining a chemical precipitation method with a calcination method, and then adding acid acidification, a mordant and an organic activator into a reaction solution to form an acidified composite crystal transformation solution. The acidified composite crystal transformation solution effectively promotes the generation of high-quality gypsum whiskers.
(3) The process has wide and simple raw material sources, changes industrial by-product gypsum into calcium sulfate whisker, calcium oxide and the like, generates high value-added products, and obtains calcium oxide with the purity of more than 99 percent and the calcium sulfate whisker with the purity of more than 99 percent and the length-diameter ratio of 150-160.
(4) The treated precipitate is used for preparing calcium oxide, the filtrate is used for preparing high-quality calcium sulfate whiskers, the recycling of mother liquor is realized, and the comprehensive utilization rate of gypsum raw materials is greatly improved.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
100 parts of phosphogypsum is added with 200 parts of deionized water for washing, and the washing is repeated for 5 times. Adding 2 times of grinding medium into the gypsum after water washing, and carrying out ball milling for 8 hours. And then adding 0.5mol/L hydrochloric acid solution to fully dissolve the gypsum, adding n-hexane accounting for 5% of the mass of the gypsum to perform extraction separation, then recrystallizing, and separating to obtain pretreated gypsum.
Adding water with the mass being 3 times of that of the pretreated gypsum, stirring and dispersing to prepare a suspension, and then mixing the gypsum, ammonium bicarbonate and ammonia water according to a molar ratio of 1: 1.15: 1.2 adding 0.5mol/L ammonium bicarbonate solution and 1mol/L ammonia water to react for 2 hours at 40 ℃ under the stirring condition of 150r/min, filtering out precipitates after complete reaction, cleaning and drying to obtain calcium carbonate, and calcining the calcium carbonate at 900 ℃ to obtain calcium oxide with the purity of 99.3 percent; the separated reaction solution is ready for use.
And adding water into the reaction solution for dilution by 5 times, adding hydrochloric acid, and acidifying to obtain a solution with the pH value of 1. Then adding magnesium chloride accounting for 10 wt% of the mass of the reaction liquid and polyacrylamide accounting for 3 wt% of the mass of the reaction liquid into the reaction liquid, and uniformly mixing to form the acidified composite crystal transformation solution. The mass ratio of the pretreated gypsum to the solution is 1:50, the gypsum and the solution react for 3 hours in a synthesis reactor at the temperature of 120 ℃ and the rotating speed of 200r/min, and the gypsum and the solution are subjected to ultrasonic action for 10 minutes. After the reaction is finished, filtering, washing the generated calcium sulfate whisker by using ethanol, and drying at 120 ℃ for 2 hours. The calcium sulfate crystal whisker with the purity of 99.1 percent and the average length-diameter ratio of 155 is obtained, and the comprehensive utilization rate of the gypsum raw material is 99 percent.
Example 2
100 parts of desulfurized gypsum are taken and added with 400 parts of deionized water for washing, and the washing is repeated for 2 times. Adding 2.5 times of grinding medium into the gypsum after water washing, and carrying out ball milling for 6 hours. And then adding 0.5mol/L hydrochloric acid solution to fully dissolve the gypsum, adding ethyl acetate with the mass of 8% of that of the gypsum to extract and separate the gypsum, and then recrystallizing the gypsum to obtain pretreated gypsum.
Adding water with the mass being 2 times of that of the pretreated gypsum, stirring and dispersing to prepare a suspension, and then mixing the suspension with gypsum, sodium bicarbonate and ammonia water in a molar ratio of 1: 1.15: 1.2 adding 0.8mol/L sodium bicarbonate solution and 0.5mol/L ammonia water solution, reacting for 3 hours at 60 ℃ under the stirring condition of 120r/min, filtering out precipitates after complete reaction, cleaning and drying to obtain calcium carbonate, and calcining the calcium carbonate at 1000 ℃ to obtain calcium oxide with the purity of 99.5 percent; the separated reaction solution is ready for use.
And adding water into the reaction solution for dilution by 5 times, adding hydrochloric acid, and acidifying to obtain a solution with the pH value of 2. Then adding 15% of zinc chloride and 5% of polypropylene glycol into the reaction solution, and uniformly mixing to form an acidified composite crystal transformation solution. The mass ratio of the pretreated gypsum to the solution is 1:30, the gypsum and the solution react for 2 hours in a synthesis reactor at the temperature of 130 ℃ and the rotating speed of 300r/min, and the gypsum and the solution are subjected to ultrasonic action for 20 minutes. After the reaction is finished, filtering, washing the generated calcium sulfate whisker by using ethanol, and drying at 130 ℃ for 2 hours. The calcium sulfate crystal whisker with the purity of 99.3 percent and the average length-diameter ratio of 151 is obtained, and the comprehensive utilization rate of the gypsum raw material is 99 percent.
Example 3
And adding 300 parts of deionized water into 100 parts of fluorgypsum, washing with water, and repeating the washing for 3 times. And adding 3 times of grinding medium into the gypsum after water washing, and carrying out ball milling for 4 hours. Then adding 0.5mol/L hydrochloric acid solution to fully dissolve the gypsum, adding n-butanol with the mass of 4% of that of the gypsum to extract and separate, then recrystallizing, and separating to obtain the pretreated gypsum.
Adding water with the mass of 5 times of that of the pretreated gypsum, stirring and dispersing to prepare a suspension, and then mixing the suspension with the gypsum, potassium bicarbonate and ammonia water in a molar ratio of 1: 1.15: 1.2 adding 1mol/L potassium bicarbonate solution and 0.1mol/L ammonia water solution, reacting for 1 hour at 50 ℃ under the stirring condition of 200r/min, filtering out precipitates after complete reaction, cleaning and drying to obtain calcium carbonate, and calcining the calcium carbonate at 950 ℃ to obtain calcium oxide with the purity of 99.1 percent; the separated reaction solution is ready for use.
And adding water into the reaction solution for dilution by 5 times, adding hydrochloric acid, and acidifying to obtain a solution with the pH value of 1.2. Then adding 8% of copper chloride and 1% of methoxypolyethylene glycol into the reaction solution, and uniformly mixing to form an acidified composite crystal transformation solution. The mass ratio of the pretreated gypsum to the solution is 1:10, the gypsum and the solution react for 3 hours in a synthesis reactor at the temperature of 110 ℃ and the rotating speed of 500r/min, and the gypsum and the solution are subjected to ultrasonic action for 30 minutes. After the reaction is finished, filtering, washing the generated calcium sulfate whisker by using ethanol, and drying at 150 ℃ for 1 hour. The calcium sulfate crystal whisker with the purity of 99.0 percent and the average length-diameter ratio of 158 is obtained, and the comprehensive utilization rate of the gypsum raw material is 99 percent.
Claims (10)
1. A method for preparing high-quality calcium sulfate whisker and calcium oxide by using industrial byproduct gypsum is characterized by comprising the following steps: the method comprises the following steps:
1) pretreatment: washing industrial byproduct gypsum with water, performing ball milling on the washed gypsum, adding a hydrochloric acid solution for dissolving after ball milling, adding an organic solvent for extraction and separation after dissolving, and then recrystallizing to obtain pretreated gypsum;
2) preparation of calcium oxide: adding water into the pretreated gypsum in the step 1) and uniformly stirring to prepare suspension; adding bicarbonate and ammonia water into the suspension, reacting for 1-3 hours under the stirring condition of 100-200r/min, filtering after the reaction is completed, and filtering to obtain filtrate for later use; washing and drying the precipitate to obtain calcium carbonate, and calcining the calcium carbonate to obtain calcium oxide;
3) preparing calcium sulfate whiskers: adding water and hydrochloric acid into the filtrate obtained in the step 2), adding a habit modifier and an organic active agent into the acidified reaction liquid to form an acidified composite crystal transformation solution, adding pretreated gypsum into the acidified composite crystal transformation solution, reacting for 1-5 hours at the temperature of 100-150 ℃ and the rotating speed of 100-500 r/min, performing ultrasonic action, filtering, washing and drying to obtain the calcium sulfate whisker.
2. The method of claim 1, wherein: the adding amount of the grinding medium in the step 1) is 2-3 times of the mass of the industrial byproduct gypsum, the grinding time is 4-10 hours, and the average particle size of the ground gypsum is less than 30 mu m.
3. The method of claim 1, wherein: the organic solvent in the step 1) is one or more of n-hexane, ethyl acetate and n-butanol.
4. The method of claim 1, wherein: the mass ratio of the gypsum to the water pretreated in the step 2) is 1: 2-1: 5.
5. the method of claim 1, wherein: the mol ratio of the gypsum, the bicarbonate and the ammonia water after pretreatment in the step 2) is 1: 1.15: 1.2, adding the bicarbonate solution with the concentration of 0.2-1mol/L, wherein the concentration of ammonia water is 0.1-1mol/L, and the reaction temperature is 40-60 ℃.
6. The method of claim 5, wherein: the bicarbonate is one or more of ammonium bicarbonate, sodium bicarbonate and potassium bicarbonate.
7. The method of claim 1, wherein: the calcination temperature of the calcium carbonate is 850-1000 ℃.
8. The method of claim 1, wherein: the pH value of the reaction solution after acidification in the step 3) is 1-2.
9. The method of claim 1, wherein: in the step 3), the medium crystal agent is one or more of magnesium chloride, zinc chloride or copper chloride, and the addition amount is 5-20 wt% of the mass of the acidified reaction liquid; the organic activator is one or more of polyacrylamide, polypropylene glycol or methoxy polyethylene glycol, and the addition amount is 1 to 5 weight percent of the mass of the reaction liquid after acidification.
10. The method of claim 1, wherein: the mass ratio of the gypsum pretreated in the step (3) to the acidified composite crystal transformation solution is 1: 10-50, and the ultrasonic action time is 10-30 minutes.
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